CN103748143A - Polyamide 1010 resin particles and method for producing same - Google Patents

Abstract

The production of polyamide 1010 resin particles, in which polyamide 1010 resin, a different polymer (B), and an organic solvent are dissolved and mixed and thereupon an emulsion is formed within a system for phase-separation into two phases, being a solution phase having the polyamide 1010 resin as the main component and a solution phase having the polymer (B) as the main component, and thereafter a poor solvent of the polyamide 1010 resin is brought into contact therewith to precipitate the polyamide 1010 resin, wherein the formation of the emulsion is implemented at a temperature of 100 DEG C or greater, thereby making it possible to obtain highly crystalline polyamide 1010 particles having high sphericity.

Description

Polyamide 1010 resin particle and manufacture method thereof

Technical field

The present invention relates to polyamide 1010 resin particle and manufacture method thereof, in more detail, relate to surface smoothness excellence, spherical shape, powder fluidity is good, polyamide 1010 resin particle and the manufacture method thereof of excellent rigidity.

Background technology

So-called resin particle, is the particle by resin formation, is generally that its diameter is that tens nm are to the big or small particle miscellaneous of hundreds of μ m.Resin particle is different from the forming polymer product such as film, fiber, injection-molded article, extrusion molding article, and its specific surface area is large, by utilizing the structure of particulate to can be used for modification, the improvement of various materials.

As main application, can enumerate the properties-correcting agent of makeup, for toning agent the rheology modifier, medical-diagnosis of additive, coating etc. check agent, to the additive of the products formeds such as automotive material, material of construction etc.Particularly it uses as the raw material of rapid shaping (rapid prototyping), manufacture (Rapid Manufacturing) fast gradually in recent years, described rapid shaping, to manufacture be fast the microgranular texture that utilizes resin particle, combines to make the method for the products formed of customization with laser processing technology.

In recent years, take in the field of fields such as electronic information material that liquid-crystal display is representative, makeup, coating, for this resin particle, require to compare with present situation characteristic, the higher functions such as resin particle of the more uniform form of size distribution, high-precision resin particles such as thering is better thermotolerance, solvent resistance always.

In resin particle; polyamide particles is due to the features such as water absorbability of its raw-material intensity, appropriateness; therefore in the field of makeup, coating, used since ancient times; but the viewpoint of protecting from global environment in recent years; its raw material sources are accelerated in variation biomass, non-petroleum; particularly, from the acquired viewpoint of raw-material functional performance, raw material, polyamide 1010 resin particle receives publicity.

In the manufacturing process of polyamide 1010 resin particle, generally speaking, use the method for the particle of polyamide 1010 resin being carried out to mechanical disintegration, but low in degree of sphericity by pulverizing the particle obtaining, there is problem in the wide aspect of size-grade distribution.

As the method that they are improved, in patent documentation 1, proposed, polyamide resin and water-soluble composition are carried out to melting mixing, after mixing, solvable composition water is removed, thereby manufacture the method for polyamide resin particle, although obtained spherical particle, the residual problem of powder fluidity.

In addition, as take patent documentation 2 as representative, proposed polyamide resin to heat in alcohol equal solvent and be dissolved in solvent, while the temperature that reduces solvent, separate out the method for polyamide resin particle, but present situation is that the particle that discloses gained is Porous, at aspects such as powder fluidities, require the technology (patent documentation 2,3,4) as the further improvement of functional particle.

On the other hand, as the method that forms resin particle, in patent documentation 5, proposed, by two or more resin dissolves, the emulsion that utilization is obtained by the phenomenon of phase separation of macromolecular solution, obtain the method for resin particle, but about the particlized of the polyamide resin as crystalline polymer, technique improvement is necessary.

Prior art document

Patent documentation

Patent documentation 1: No. 2007-277546, TOHKEMY

Patent documentation 2: No. 2010-163618, TOHKEMY

Patent documentation 3: No. 2011-218330, TOHKEMY

Patent documentation 4: No. 2011-219756, TOHKEMY

No. 5:WO2009/142231, patent documentation

Summary of the invention

Invent problem to be solved

In the manufacture method of polyamide 1010 resin particle up to now, there is problem in the mobility of polyamide 1010 resin particle, sliding etc., in addition in the method that particle is Porous, except powder fluidity, also there is problem in physical strength, the aspects such as particle collapse occurs in use and have problem.

It is high that problem of the present invention is to provide formation degree of sphericity, the shape that degree of crystallinity is high, the polyamide 1010 resin particle of the mechanical characteristics excellences such as powder fluidity, rigidity.

For solving the method for problem

In order to realize above-mentioned problem, the inventor etc. conduct in-depth research, and result has realized following invention.

That is, the present invention is:

" (1) a kind of polyamide 1010 resin particle, is characterized in that, median size is 1～100 μ m, and degree of sphericity is more than 80, through wide-angle x-ray scattering, measure, and at diffraction angle 2 θ, be that 24 degree places have peak,

(2) according to the polyamide 1010 resin particle (1) described, it is characterized in that, through wide-angle x-ray scattering, measure, is that 20 degree and 24 degree places have peak at diffraction angle 2 θ,

(3) according to the polyamide 1010 resin particle (1) or (2) described, it is characterized in that, the slope of repose of powder is below 30 °,

(4) according to the polyamide 1010 resin particle described in any one of (1)～(3), it is characterized in that, the compressive modulus of elasticity of the particle being obtained by micro-compression testing machine is more than 1.6GPa,

(5) according to the polyamide 1010 resin particle described in any one of (1)～(4), it is characterized in that, while measuring with beam splitting type chromascope, lightness L value is more than 70,

(6) a kind of manufacture method of polyamide 1010 resin particle, it is characterized in that, make can be separated into after polyamide 1010 resin, polymer B except polyamide 1010 resin and organic solvent dissolution are mixed using polyamide 1010 resin as the solution phase of principal constituent and the polymer B of usining except polyamide 1010 resin the System forming emulsion as this two-phase of solution phase of principal constituent, then make this emulsion contact with the poor solvent of polyamide 1010 resin, polyamide 1010 resin is separated out, in more than 100 ℃ temperature, implement the formation of emulsion

(7) according to the manufacture method of the polyamide 1010 resin particle (6) described, it is characterized in that, the SP value of the polymer B except polyamide 1010 resin is 20 (J/cm ³) ^1/2above,

(8) according to the manufacture method of the polyamide 1010 resin particle (6) or (7) described, it is characterized in that, the solubleness in water in the time of 25 ℃ of the polymer B except polyamide 1010 resin is more than 1g/100g,

(9) according to the manufacture method of the polyamide 1010 resin particle described in any one of (6)～(8), it is characterized in that, polymer B except polyamide 1010 resin in its molecular skeleton, have in hydroxyl, ether, amide group, carboxyl at least any

(10) according to the manufacture method of the polyamide 1010 resin particle described in any one of (6)～(9), it is characterized in that, polymer B except polyamide 1010 resin is any in polyvinyl alcohol, hydroxy alkyl cellulose, polyalkylene glycol, polyvinylpyrrolidone, water-soluble nylon, polyacrylic acid

(11) according to the manufacture method of the polyamide 1010 resin particle described in any one of (6)～(10), it is characterized in that, polymer B except polyamide 1010 resin is polyvinyl alcohol, and the sodium acetate content in polyvinyl alcohol is below 0.1 quality %

(12) according to the manufacture method of the polyamide 1010 resin particle described in any one of (6)～(10), it is characterized in that, polymer B except polyamide 1010 resin is polyvinyl alcohol, adds acid compound when emulsion forms in system

(13) according to the manufacture method of the polyamide 1010 resin particle (12) described, it is characterized in that, the acid compound adding is that the 1st dissociation index (pKa1) is the acid below 4.5, more than the boiling point that its decomposition temperature is poor solvent,

(14) according to the manufacture method of the polyamide 1010 resin particle (12) or (13) described, it is characterized in that, the acid compound adding be selected from citric acid, tartrate, propanedioic acid, oxalic acid, hexanodioic acid, toxilic acid, oxysuccinic acid, phthalic acid, succsinic acid, polyacrylic acid more than a kind

(15) according to the manufacture method of the polyamide 1010 resin particle described in any one of (6)～(14), it is characterized in that, the SP value of organic solvent is 20 (J/cm ³) ^1/2above and boiling point be more than 100 ℃,

(16) according to the manufacture method of the polyamide 1010 resin particle described in any one of (6)～(15), it is characterized in that, organic solvent is for being selected from N-Methyl pyrrolidone, methyl-sulphoxide, N, dinethylformamide, N, N-N,N-DIMETHYLACETAMIDE, 1, in 3-dimethyl-2-imidazolidone more than a kind

(17) according to the manufacture method of the polyamide 1010 resin particle described in any one of (6)～(16), it is characterized in that, after emulsion forms, in order to make polyamide 1010 resin, separate out, temperature while contacting with poor solvent is temperature more than the decrease temperature crystalline temperature of polyamide 1010 resin

(18) according to the manufacture method of the polyamide 1010 resin particle described in any one of (6)～(17), it is characterized in that, after polyamide 1010 resin is separated out, carry out solid-liquid separation and remove polyamide 1010 resin particle, from the remaining solution that comprises the polymer B composition except polyamide 1010 resin, remove poor solvent, in the solution of gained, again add polyamide 1010 resin, formation can be separated into using polyamide 1010 resin as the solution phase of principal constituent and the polymer B of usining except polyamide 1010 resin the system as this two-phase of solution phase of principal constituent, organic solvent and the polymer B except polyamide 1010 resin are recycled.”。

The effect of invention

Polyamide 1010 resin particle of the present invention is spherical shape and has high crystalline, therefore powder fluidity, excellent rigidity, therefore such as in fields such as cosmetic use, coating, due to smooth sense of touch and long-term quality stability excellence, in addition, high chemical resistance is excellent, therefore the interpolation material of the lubricant by the sliding component as engine etc., thereby become the damage that can suppress sliding component, useful material in the industries such as while long term maintenance sliding.

Accompanying drawing explanation

The X ray mensuration that Fig. 1 is the polyamide 1010 resin particle manufactured by embodiment 1 is schemed.

The X ray mensuration that Fig. 2 is the polyamide 1010 resin particle manufactured by embodiment 2 is schemed.

The X ray mensuration that Fig. 3 is the polyamide 1010 resin particle manufactured by embodiment 3 is schemed.

The X ray mensuration that Fig. 4 is the polyamide 1010 resin particle manufactured by comparative example 1 is schemed.

The X ray mensuration that Fig. 5 is the polyamide 1010 resin particle manufactured by comparative example 2 is schemed.

The X ray mensuration that Fig. 6 is the polyamide 1010 resin particle manufactured by comparative example 3 is schemed.

Fig. 7 is for representing the polyamide 1010 resin particle of being manufactured by embodiment 1 with scanning electron microscope with 1000 times of figure that carry out observable result of multiplying power.

Fig. 8 is for representing the polyamide 1010 resin particle of being manufactured by embodiment 2 with scanning electron microscope with 1000 times of figure that carry out observable result of multiplying power.

Fig. 9 is for representing the polyamide 1010 resin particle of being manufactured by embodiment 3 with scanning electron microscope with 1000 times of figure that carry out observable result of multiplying power.

Figure 10 is for representing the polyamide 1010 resin particle of being manufactured by comparative example 1 with scanning electron microscope with 1000 times of figure that carry out observable result of multiplying power.

Figure 11 is for representing the polyamide 1010 resin particle of being manufactured by comparative example 2 with scanning electron microscope with 100 times of figure that carry out observable result of multiplying power.

Figure 12 is for representing the polyamide 1010 resin particle of being manufactured by comparative example 3 with scanning electron microscope with 30 times of figure that carry out observable result of multiplying power.

Embodiment

Below, the present invention is described in detail.

Polyamide 1010 resin particle of the present invention, is characterized in that, the median size of particle is 1～100 μ m, through wide-angle x-ray scattering, at diffraction angle 2 θ, is that 24 degree places have peak.

So-called polyamide 1010 resin particle of the present invention is the particle being formed by polyamide 1010 resin.So-called polyamide 1010 resin, is nylon 1010, is to be polymerized by the 1，10-diaminodecane of aliphatie diamine and the sebacic acid of aliphatic dicarboxylic acid.

Polyamide 1010 resin can obtain by known method in the past, for example, can obtain by the melt polymerization using the salt of above-mentioned diamines and dicarboxylic acid as raw material, solution polymerization, and obtain by solid state polymerization using low molecular polyamides 1010 as raw material etc.

As the decamethylene diamine of raw material, the raw material that sebacic acid origin comes from oil, the raw material that derives from biomass, by chemical conversion, obtain, be not particularly limited in the present invention, the viewpoint from global environment protection, is preferably the raw material that derives from biomass.

The polymerization degree of polyamide 1010 resin is not particularly limited, from the viewpoint of the rigidity of the resin particle of gained, as weight-average molecular weight, under it, be limited to 1, more than 000, be preferably more than 5,000, more preferably 10, more than 000, more preferably more than 12,000, be particularly preferably more than 15,000.In addition, as its upper limit, be 1,000, below 000, be preferably below 500,000, more preferably, below 100,000, more preferably, below 50,000, be particularly preferably below 30,000.Here, weight-average molecular weight refers to by having used hexafluoroisopropanol to measure as the gel permeation chromatography (GPC) of solvent, the value that converts and obtain with polymethylmethacrylate.

The median size of the polyamide 1010 resin particle in the present invention refers to the median size of the scope of 1 μ m～100 μ m, as its preferred upper limit, be below 80 μ m, more preferably below 60 μ m, more preferably, below 50 μ m, be particularly preferably below 30 μ m.In addition more than being limited to 1.0 μ m under it, being preferably and surpassing 1.0 μ m, more preferably more than 5 μ m, more preferably surpass 5 μ m, more than being particularly preferably 10 μ m, being preferably significantly and surpassing 10 μ m.

In addition, the median size of so-called polyamide 1010 resin particle of the present invention, is by by specific 100 particle dias arbitrarily of scanning electron microscope photo, obtains that its arithmetical mean calculates.In above-mentioned photo, at this particle, not in orbicular situation,, in oval such situation, the maximum diameter of particle is made as to its particle diameter.In order to measure exactly particle diameter, be amplified at least 500 times above, be preferably 1000 times of above multiplying powers, carry out the mensuration of particle diameter.

In addition the narrow particle size distribution of preferred its particle of polyamide 1010 resin particle of the present invention.Size-grade distribution can be with the size distribution exponential representation in mathematical expression described later (2).The particle size distribution index of polyamide 1010 resin particle of the present invention is below 3, is preferably below 2.5, more preferably, below 2.0, more preferably, below 1.8, is particularly preferably below 1.5, is preferably below 1.3 significantly.In addition, preferred lower limit is not special, is limited to more than 1 in theory under it.

Polyamide 1010 resin particle characteristics of the present invention is that degree of sphericity is high, because degree of sphericity is high, therefore thinks and can show good mobility.

So-called degree of sphericity in the present invention, can measure minor axis and the major diameter of 30 particles arbitrarily by scanning electron microscope photo, uses the value representation of calculating according to following mathematical expression (1), can say more higher close to 100 degree of sphericity.

[mathematical expression 1]

Wherein, n: measure several 30.

The degree of sphericity of polyamide 1010 resin particle of the present invention is more than 80, is preferably more than 85, more preferably more than 90, more preferably more than 95.As the preferred upper limit, be below 100, even but be conventionally below 90, also can obtain the effect fully such as sliding, smooth texture raising.In the situation that degree of sphericity is less than 80, ball, close to ellipse, can not get smooth sense of touch.

Polyamide 1010 resin particle characteristics in the present invention is that crystallinity is very high, and due to this characteristic, the modular ratio therefore with resin particle is high such characteristic in the past.The degree of crystallinity height can be measured to judge by carrying out powder X-ray ray, polyamide 1010 resin particle of the present invention, in the Alpha-ray wide-angle x-ray scattering of the K that has used copper atom (Cu) is measured, is that distinctive 20 degree and 24 degree places have peak at diffraction angle 2 θ.

Particularly, through wide-angle x-ray scattering, the distinctive peak of the peak of the degree of 24 in diffraction angle 2 θ for observing when the crystalline structure growth of polyamide 1010 resin, this polyamide 1010 resin particle has this peak.

In addition, although polyamide 1010 resin particle crystalline structure growth of the present invention, as its shape, because degree of sphericity is high, therefore have both good fluidity, the low such feature in slope of repose of powder.

The slope of repose of the powder being formed by polyamide 1010 resin particle of the present invention is below 30 °, is preferably below 25 °, more preferably below 20 °, more preferably below 15 °.The lower limit at slope of repose is not special, but over 0 °.

Polyamide 1010 resin particle of the present invention is because crystallinity is high, thus its to have physical strength high, the feature that Young's modulus is high.

The Young's modulus of the polyamide 1010 resin particle in the present invention is more than 1.6GPa, more than being preferably 1.7GPa, more preferably more than 1.8GPa, more preferably more than 1.9GPa, more than being particularly preferably 2.0GPa.

In order to obtain the Young's modulus of particle-like substance, can use the theory of elasticity of hertz (hertz) by using the micro-compression testing machine of Shimadzu Corporation's system, calculate its Young's modulus.

By having high like this Young's modulus, the scope of application in sliding component etc. expands, and therefore becomes as the useful material of resin particle.

Polyamide 1010 resin particle of the present invention is due to crystalline structure growth, therefore reflection of light is except the reflection at particle interface place, also result from the reflection of crystalline structure of inside particles, be therefore characterised in that and particularly when measuring with beam splitting type chromascope, represent that the L value of lightness uprises.

L value as representing lightness, is preferably more than 70, more preferably more than 80, is particularly preferably more than 85.In the situation that L value is less than 70, it is large that painted factor becomes, and for cosmetic use, coating purposes etc. in the situation that, is difficult to form color and luster arbitrarily.On L value preferred, be limited to 100.

Polyamide 1010 resin particle characteristics of the present invention is the spherical shape into surface smoothness.Here so-called surface smoothness, the surperficial photo of the particle that can be obtained by the morphologic observation that utilizes scanning electron microscope photo, concavo-convex number that can visual judgement by instrumentation carries out quantification.Preferably every 1 particle is below 20, more preferably below 10.

In addition, above-mentioned surface smoothness is, in the region of observing by the multiplying power of 1000～5000 times of scanning electron microscope photo, 30 Arbitrary Particles of observation concavo-convex, is determined by its mean value.

When manufacture has the polyamide 1010 resin particle of superperformance as described above, can adopt method shown below.

The manufacture method of the polyamide 1010 resin particle the present invention relates to, it is characterized in that, make polyamide 1010 resin, polymer B except polyamide 1010 resin and organic solvent dissolution mix and can be separated into that to using polyamide 1010 resin (following as the solution phase of principal constituent, be sometimes referred to as polyamide 1010 resin solution phase) and the polymer B of usining except polyamide 1010 resin (following as the solution phase of principal constituent, be sometimes referred to as polymer B solution phase) the System forming emulsion of this two-phase, then make this emulsion contact with the poor solvent of polyamide 1010 resin, thereby polyamide 1010 resin is separated out.

As the polymer B except polyamide 1010 resin in the present invention, can enumerate thermoplastic resin, thermosetting resin, but from dissolving in order to form solution phase, the viewpoint that is easy to obtain the state be separated into two-phase is set out, be preferably thermoplastic resin, for ease of obtaining the state that is separated into two-phase, as the polymer B except polyamide 1010 resin in the present invention, preferably its SP value is 20 (J/cm ³) ^1/2above.

Polymer B except above-mentioned polyamide 1010 resin if, be easy to form the phase-separated state of polymer B solution phase and polyamide 1010 resin solution phase, and when separating out by poor solvent described later, because separating out of the polymer B except polyamide 1010 resin is difficult to occur, therefore can not form and bring detrimentally affect particle.

Now, the SP value as the polymer B except polyamide 1010 resin, is preferably 21 (J/cm ³) ^1/2above, 23 (J/cm more preferably ³) ^1/2above, 25 (J/cm more preferably ³) ^1/2above, be particularly preferably 28 (J/cm ³) ^1/2above, be extremely preferably 30 (J/cm ³) ^1/2above.

As long as the two is dissolved in polyamide 1010 resin and polymer B except polyamide 1010 resin in organic solvent, be not particularly limited, the upper limit as the difference of SP value, is preferably 20 (J/cm ³) ^1/2below, 15 (J/cm more preferably ³) ^1/2below, 10 (J/cm more preferably ³) ^1/2below.

Here so-called SP value, the value calculating for the predication method based on Fedor, for the value that calculates based on cohesive energy density(CED) and molar volume (following, be sometimes referred to as computing method.) (" と Meter calculation method for SP value base Foundation ying " Yamamoto show tree work, the apparatus of information of Co., Ltd., puts down into distribution on March 31st, 17).

In the situation that can not calculating by aforesaid method, the laboratory method that can whether dissolve for the known solvent of solubility parameter by judgement is calculated SP value and (below, is sometimes referred to as laboratory method.), use it to replace (" Polymer Handbook Fourth Edition " J.Brand work, the distribution in 1998 of Wiley society).

Wherein, the polymer B except polyamide 1010 resin is preferably the polymkeric substance high with the affinity of poor solvent described later, as the index of its affinity, can judge with the solubleness in water.Solubleness about the polymer B except polyamide 1010 resin in water, in the situation that being expressed as 1g/100g when dissolving 1g at 25 ℃ in water 100g and defining, more than being preferably 1g/100g, more preferably more than 2g/100g, more preferably more than 5g/100g, more than being particularly preferably 10g/100g, more than being preferably 15g/100g significantly.As long as for this scope, high with the affinity of poor solvent described later, in this polyamide 1010 resin particle manufacturing process, advantageously work.

As the high molecular kind of the polymer B except polyamide 1010 resin, as concrete preferred kind, be preferably in its molecular skeleton, have in hydroxyl, ether, amide group, carboxyl at least any.

If the polymer B of illustration except polyamide 1010 resin,, as have the polymkeric substance of hydroxyl in its molecular skeleton, can enumerate polyvinyl alcohol (fully saponified type particularly, poly-(vinyl alcohol) of partly-hydrolysed type, fully saponified type, poly-(vinyl alcohol-ethene) copolymer analogs such as poly-(vinyl alcohol-ethene) multipolymer of partly-hydrolysed type etc.), poly-(4-Vinyl phenol), maltose, cellobiose, lactose, the disaccharides such as sucrose, Mierocrystalline cellulose and derivative thereof (hydroxy alkyl cellulose (hydroxy ethyl cellulose, hydroxy propyl cellulose, EHEC etc.), Mierocrystalline cellulose, methylcellulose gum, ethyl cellulose, carboxy methyl ethyl cellulose, carboxy methyl cellulose, sodium carboxy methyl cellulose, cellulose ester, chitosan etc.), amylose starch and derivative thereof, starch and derivative thereof, dextrin, cyclodextrin, the polyose such as sodiun alginate and derivative thereof or derivatives thereof, gelatin, casein, collagen, albumin, fibroin, Keratin sulfate, scleroproein, carrageenan, chondroitin sulfate, Sudan Gum-arabic, agar, protein etc., as have the polymkeric substance of ether in its molecular skeleton, can enumerate polyalkylene glycol, sucrose fatty ester, poly-(oxygen ethene fatty acid ester), poly-(oxygen ethene lauric fatty acid esters), poly-(oxygen ethylene glycol mono fatty acid ester), poly-(oxygen vinyl alkyl phenyl ether), poly-(oxyalkyl ether), polyvingl ether, polyvinyl formals etc., as have the polymkeric substance of amide group in its molecular skeleton, can enumerate polyvinylpyrrolidone, amino poly-(acrylamide), poly-(acrylamide), poly-(Methacrylamide), " AQ Na イ ロ Application (registered trademark) " (A-90, P-70, P-95, T-70, Dongレ Co., Ltd. system) water-soluble nylon etc. such as, as there is the polymkeric substance of carboxyl in its molecular skeleton, can enumerate polyacrylic acid, sodium polyacrylate, polymethyl acrylic acid, sodium polymethacrylate etc., in addition, can enumerate the synthetic resins such as polystyrolsulfon acid, sodium polystyrene sulfonate, polyvinyl chlorination tetramethyleneimine, poly-(styrene-maleic acid) multipolymer, PAH, poly-(oxygen vinyl-amine), poly-(vinyl pyridine), poly-amino sulfone, polymine.

Be preferably polyvinyl alcohol (fully saponified type, poly-(vinyl alcohol) of partly-hydrolysed type, fully saponified type, poly-(vinyl alcohol-ethene) copolymer analogs such as poly-(vinyl alcohol-ethene) multipolymer of partly-hydrolysed type), derivatived cellulose (carboxy methyl cellulose, hydroxy alkyl cellulose (hydroxy ethyl cellulose, hydroxy propyl cellulose, EHEC), methylcellulose gum, ethyl cellulose, carboxy methyl ethyl cellulose, carboxy methyl cellulose, sodium carboxy methyl cellulose, cellulose ester etc.), polyalkylene glycol, sucrose fatty ester, poly-(oxygen vinyl alkyl phenyl ether), poly-(oxyalkyl ether), polyvinylpyrrolidone, water-soluble nylon, polyacrylic acid, polymethyl acrylic acid, more preferably poly-(vinyl alcohol) class (fully saponified type, poly-(vinyl alcohol) of partly-hydrolysed type, fully saponified type, poly-(vinyl alcohol-ethene) copolymer analogs such as poly-(vinyl alcohol-ethene) multipolymer of partly-hydrolysed type), derivatived cellulose (carboxy methyl cellulose, hydroxy alkyl cellulose (hydroxy ethyl cellulose, hydroxy propyl cellulose, EHEC), methylcellulose gum, ethyl cellulose, carboxy methyl ethyl cellulose, carboxy methyl cellulose, sodium carboxy methyl cellulose, cellulose ester etc.), polyalkylene glycol, polyvinylpyrrolidone, water-soluble nylon, polyacrylic acid, is particularly preferably fully saponified type, polyvinyl alcohols such as poly-(vinyl alcohols) of partly-hydrolysed type, hydroxy ethyl cellulose, the hydroxy alkyl celluloses such as hydroxy propyl cellulose, polyalkylene glycol, polyvinylpyrrolidone, water-soluble nylon, polyacrylic acid.

As the polymer B except polyamide 1010 resin in the present invention, preferably use significantly polyvinyl alcohol.Say that in further detail so-called polyvinyl alcohol refers to the polymkeric substance in molecule with the structure of following general formula (1).

Can enumerate poly-(vinyl alcohol) (can be poly-(vinyl alcohol) of fully saponified type, partly-hydrolysed type.Sometimes referred to as polyvinyl alcohol.), poly-(vinyl alcohol-ethene) multipolymer (can be poly-(vinyl alcohol-ethene) multipolymer of fully saponified type, partly-hydrolysed type) etc., from solvability aspect, be preferably polyvinyl alcohol.

The molecular weight of the polymer B except polyamide 1010 resin preferably counts 1,000～100 with weight-average molecular weight, and 000,000, more preferably 1,000～10,000,000, more preferably 5,000～1,000,000, be particularly preferably 10,000～500,000 scope, most preferred scope is 10,000～100,000 scope.

Here so-called weight-average molecular weight, refers to by water is measured as the gel permeation chromatography (GPC) of solvent, the weight-average molecular weight that converts and obtain with polyoxyethylene glycol.

In the situation that can not water measuring, use dimethyl formamide, in the situation that however can not measuring, use tetrahydrofuran (THF), in the situation that can't measuring, use hexafluoroisopropanol.

About polyvinyl alcohol, generally after polymerization, under alkaline condition, be hydrolyzed by carrying out vinyl-acetic ester as raw material, thereby generation polyvinyl alcohol, wherein, common a part of sodium acetate is residual as impurity, also conventionally comprises 0.2 quality % left and right in commercially available product.

Find in the present invention, the contained sodium acetate of above-mentioned polyvinyl alcohol has impact under some form, while forming emulsion polyamide 1010 resin and organic solvent dissolution are mixed, if its temperature is more than 100 ℃, particulate is painted, or the deteriorated and recirculation of polyvinyl alcohol worsens.

That is,, about the polyvinyl alcohol as polymer B except polyamide 1010 resin, even for also stabilization under the micronize condition more than 100 ℃, preferably allow to form existing sodium acetate amount reduction in the system of emulsion.As the method for reducing sodium acetate amount, preferably polyethylene alcohols is used the poor polyvinyl alcohol of sodium acetate.

The amount of the sodium acetate in the polyvinyl alcohol using in this situation, is below 0.1 mass parts with respect to polyvinyl alcohol 100 mass parts, is preferably below 0.05 mass parts, more preferably below 0.01 mass parts.

By being controlled within the scope of this, even if at high temperature carry out the micronize of polyamide 1010 resin, that also can suppress to be caused by polyvinyl alcohol decomposition, crosslinked etc. goes bad, can be by the micronize stabilization under high temperature.In addition under, preferred, be limited to 0 mass parts.

In order to obtain the poor polyvinyl alcohol of sodium acetate, for example can enumerate the method for washing with organic solvents such as methyl alcohol, ethanol; After being dissolved in water etc., precipitation in the poor solvent of polyvinyl alcohol and the reprecipitation method that generates; Ultrafiltration process; The method of removing by ion exchange resin, ion-exchange carrier etc.; Deng.

In addition, during as formation emulsion, suppress other method of the impact of sodium acetate, can enumerate the method for adding acid compound in the system that can form emulsion.Thus, can form the state that does not contain in fact sodium acetate.

As the acid compound using in the present invention, specifically can enumerate formic acid, acetic acid, valeric acid (lucky oxalic acid), butyric acid, valeric acid (acid of バ レ リ ッ Network), caproic acid, enanthic acid, sad, vinylformic acid, methacrylic acid, β-crotonic acid, oxalic acid, propanedioic acid, fumaric acid, toxilic acid, pentanedioic acid, hexanodioic acid, sebacic acid, pyruvic acid, succsinic acid, the aliphatic carboxylic acids such as polyacrylic acid, lactic acid, oxyacetic acid, L-AA, saccharosonic acid, oxysuccinic acid, shikimic acid, citric acid, hydrogenation succsinic acid, the carboxylic acid that tartrate etc. contain hydroxyl, phenylformic acid, 2-fluorobenzoic acid and positional isomers thereof, 2-chloro-benzoic acid and positional isomers thereof, 2-bromo-benzoic acid and positional isomers thereof, 2-nitrobenzoic acid and positional isomers thereof, 2-toluylic acid and positional isomers thereof, phenylium, styracin, phenylmalonic acid, phthalic acid, terephthalic acid, the aromatic carboxylic acids such as Whitfield's ointment, glycine, L-Ala, α-amino-isovaleric acid, leucine, Isoleucine, Serine, Threonine, proline(Pro), Methionin, aspartic acid, L-glutamic acid, halfcystine, methionine(Met), phenylalanine, tyrosine, Histidine, l-asparagine, glutamine, arginine, tryptophane, ornithine, the amino acid such as sarkosine, methylsulfonic acid, Phenylsulfonic acid, tosic acid and positional isomers thereof, the organic sulfonic acid such as p-hydroxybenzenyl sulfonate and positional isomers thereof class, phenyl-phosphonic acid, diphenyl phosphonic acid, diphenyl phosphoester, the organophosphorus acids such as 1-naphthyl phosphate, magnesium sulfate, magnesium chloride, ammonium chloride, the salt that ammonium sulfate etc. are formed by strong acid and weak base, hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, tetra-sodium, the mineral acids such as tripolyphosphate etc.They can use a kind or use two or more.

These acid compounds, in manufacturing process described later, as long as before the heating that is used to form emulsion starts, can add in any stage, in addition, can in raw material, add in advance to use.

Now, as the addition of acid compound, the sodium acetate contained with respect to used polyvinyl alcohol, mol ratio as acid functional group, be preferably the scope of 0.1～10 times mole, more preferably the scope of 0.2～8 times mole, the more preferably scope of 0.3～5 times mole.

The amount of the sodium acetate containing in respect to used polyvinyl alcohol at the addition of acid compound, in the very few situation of the mol ratio of acid functional group, has and carries out the crosslinked of polyvinyl alcohol, the tendency of the controlled deterioration of particle diameter in micronize operation.In addition,, when carrying out the recycling of polyvinyl alcohol, there is the tendency of the 2nd the later controlled deterioration of particle diameter.In addition, the tonal variation because the oxidation being estimated as by polyvinyl alcohol causes, therefore has the tendency that particulate variable color occurs.Therefore in addition,, in the situation that the mol ratio of acid functional group is too much, due to the impact being produced by acid, has the oxidation, decomposition of polyvinyl alcohol, crosslinked etc. tendency occur.

As the acid compound using in the method the present invention relates to, preferably using the 1st dissociation index (pKa1) of acid compound is the acid compound below 4.5.

Because the method the present invention relates to is implemented under more than 100 ℃ high temperature, therefore as acid compound used, preferably heat resisting temperature is 100 ℃ of above acid compounds.Now, so-called heat resisting temperature, refers to the decomposition temperature of this acid compound.

Wherein, as thering are 100 ℃ of above heat resisting temperatures, pKa1 is the example of the acid compound below 4.5, can use L-AA, saccharosonic acid, lactic acid, oxysuccinic acid, fumaric acid, phthalic acid, tartrate, formic acid, citric acid, oxyacetic acid, Whitfield's ointment, toxilic acid, propanedioic acid, pentanedioic acid, oxalic acid, hexanodioic acid, succsinic acid, hydrogenation succsinic acid, polyacrylic acid, L-glutamic acid, aspartic acid, arginine, ornithine, sarkosine, halfcystine, Serine, the amino acid such as tyrosine, hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, tetra-sodium, the mineral acids such as tripolyphosphate.Wherein can preferably use citric acid, tartrate, propanedioic acid, oxalic acid, hexanodioic acid, toxilic acid, oxysuccinic acid, phthalic acid, succsinic acid, polyacrylic acid.

Here so-called pKa, is the sour dissociation index of 25 ℃, refers to the logarithmic value reciprocal of the dissociation constant of the acid compound in the aqueous solution.For the pKa value of acid compound, can be with references such as chemical brief guides (revise 3 editions chemical brief guide bases compile Bian Wanshan Co., Ltd. of Japanization association publish clear and issue a magazine for 59 years).

About pKa value, from the viewpoint of convenience, in above-mentioned two methods, be preferably the method that chemical brief guide is recorded.

In the present invention, as the organic solvent that polyamide 1010 resin and the polymer B except polyamide 1010 resin are dissolved, for the organic solvent that polyamide 1010 resin and the polymer B except polyamide 1010 resin used can be dissolved, can select according to the kind of each polymkeric substance.

As concrete example, can enumerate pentane, hexane, heptane, octane, nonane, n-decane, n-dodecane, n-tridecane, hexanaphthene, the aliphatic hydrocarbon series solvents such as pentamethylene, benzene, toluene, the aromatic hydrocarbons series solvents such as dimethylbenzene, ethyl acetate, the ester series solvents such as methyl acetate, chloroform, bromofom, methylene dichloride, 1-2-ethylene dichloride, 1，1，1-trichloroethane, chlorobenzene, the halohydrocarbon series solvents such as 2,6-DCT, acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), the ketone series solvents such as methyl butyl ketone, methyl alcohol, ethanol, the alcohol series solvents such as 1-propyl alcohol-2-propyl alcohol, METHYLPYRROLIDONE, methyl-sulphoxide, DMF, N,N-dimethylacetamide, Texacar PC, trimethylammonium phosphoric acid, 1,3-dimethyl-2-imidazolidone, the non-proton property such as tetramethylene sulfone polar solvent, formic acid, acetic acid, propionic acid, butyric acid, the carboxylic acid solvents such as lactic acid, phenylmethylether, ether, tetrahydrofuran (THF), Di Iso Propyl Ether, dioxane, diglyme, the ether series solvents such as glycol dimethyl ether, or their mixture.Be preferably aromatic hydrocarbons series solvent, aliphatic hydrocarbon series solvent, halohydrocarbon series solvent, alcohol series solvent, ether series solvent, non-proton property polar solvent, carboxylic acid solvent.

As further preferred organic solvent, be that SP value is 20 (J/cm ³) ^1/2above organic solvent.Here so-called SP value, is " Polymer Handbook Fourth Edition " J.Brand work, the distribution in 1998 of Wiley society) in the value recorded of 688-701 page.

Wherein do not have the value the recorded predication method based on Fedor to calculate.This calculating is calculated and (is sometimes referred to as below, the computing method of solvent SP value based on cohesive energy density(CED) and molar volume.) (" と Meter calculation method for SP value base Foundation ying " Yamamoto show tree work, the apparatus of information of Co., Ltd., puts down into distribution on March 31st, 17).

As preferred organic solvent wherein, be the alcohol series solvent as water-soluble solvent, non-proton property polar solvent, carboxylic acid solvent, significantly preferably non-proton property polar solvent, carboxylic acid solvent.

In the present invention, owing to implementing emulsion under the high temperature more than 100 ℃, form, therefore for these solvents, also preferably thermotolerance is 100 ℃ of above solvents, and wherein the boiling point under preferred normal pressure (100kPa) is 100 ℃ of above solvents.In the situation of boiling point under this external use normal pressure lower than the solvent of 100 ℃, can be in pressure vessel use by pressurizeing.If consider such situation, from obtaining easily, and can be preferably used as the aspect that the solvent of poor solvent described later mixes equably with water, alcohol series solvent etc. sets out, most preferably be METHYLPYRROLIDONE, methyl-sulphoxide, N, dinethylformamide, N, N-N,N-DIMETHYLACETAMIDE, 1,3-dimethyl-2-imidazolidone.

These organic solvents can be used multiple, also can mix use, but particle diameter is smaller obtaining, and the particle aspect that size distribution is little, the trouble of the separated operation during from the recirculation of the solvent avoiding using, technical load in manufacture reduces such viewpoint sets out, and is preferably single organic solvent, more preferably can dissolve the two single organic solvent of polyamide 1010 resin and the polymer B except polyamide 1010 resin.

The poor solvent of the so-called polyamide 1010 resin in the present invention, refers to the solvent that can not dissolve polyamide 1010 resin.What is called can not be dissolved polyamide 1010 resin, refers to that the solubleness of polyamide 1010 resin in poor solvent is below 1 quality %, more preferably below 0.5 quality %, more preferably below 0.1 quality %.

In manufacture method of the present invention, use the poor solvent of polyamide 1010 resin, as such poor solvent, be preferably the poor solvent of polyamide 1010 resin and can dissolve the solvent of the polymer B except polyamide 1010 resin.Thus, can make polyamide 1010 resin particle efficient separates out.In addition the solvent that, preferably makes solvent that polyamide 1010 resin and the polymer B except polyamide 1010 resin are dissolved mix equably with the poor solvent of polyamide 1010 resin.

As the poor solvent in the present invention, according to polyamide 1010 resin and the combination of polymer B except polyamide 1010 resin, change, if but illustration particularly can enumerate and be selected from pentane, hexane, heptane, octane, nonane, n-decane, n-dodecane, n-tridecane, hexanaphthene, the aliphatic hydrocarbon series solvents such as pentamethylene, benzene, toluene, the aromatic hydrocarbons series solvents such as dimethylbenzene, ethyl acetate, the ester series solvents such as methyl acetate, chloroform, bromofom, methylene dichloride, 1,2-ethylene dichloride, 1，1，1-trichloroethane, chlorobenzene, the halohydrocarbon series solvents such as 2,6-DCT, acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), the ketone series solvents such as methyl butyl ketone, methyl alcohol, ethanol, the alcohol series solvents such as 1-propyl alcohol-2-propyl alcohol, methyl-sulphoxide, DMF, N,N-dimethylacetamide, trimethylammonium phosphoric acid, METHYLPYRROLIDONE, 1,3-dimethyl-2-imidazolidone, the non-proton property such as tetramethylene sulfone polar solvent, formic acid, acetic acid, propionic acid, butyric acid, the carboxylic acid solvents such as lactic acid, phenylmethylether, ether, tetrahydrofuran (THF), Di Iso Propyl Ether, dioxane, diglyme, the ether series solvents such as glycol dimethyl ether, the solvent of at least a kind in water etc.

From making the polyamide 1010 resin viewpoint of particlized efficiently, be preferably aromatic hydrocarbons series solvent, aliphatic hydrocarbon series solvent, alcohol series solvent, ether series solvent, water, be particularly preferably alcohol series solvent, water, most preferably be water.

In addition, because implementing emulsion in more than 100 ℃ temperature, the present invention forms, even therefore adopt boiling point under normal pressure lower than the solvent of 100 ℃ of grades implement situation boiling point of the present invention be 100 ℃ above also in the situation that its temperature more than boiling point is implemented emulsion forms, can in pressure vessel, under pressurized conditions, use.

In the present invention, by with respect to polyamide 1010 resin, suitably select the poor solvent of polymer B, the organic solvent that dissolves them and polyamide 1010 resin except polyamide 1010 resin to combine, thereby can make efficiently polyamide 1010 resin separate out and obtain polyamide 1010 resin particle.

Make polyamide 1010 resin, the polymer B except polyamide 1010 resin, dissolve liquid that their organic solvent mixed dissolution forms need to be separated into using polyamide 1010 resin as the solution phase of principal constituent and the polymer B of usining except polyamide 1010 resin as the solution phase of principal constituent (following, be sometimes referred to as polymer B solution phase.) this two-phase.Now, using polyamide 1010 resin as the organic solvent of the solution phase of principal constituent and the polymer B of usining except polyamide 1010 resin as the organic solvent of the solution phase of principal constituent, can be the same or different, preferably identical in fact solvent.

The condition that generates two states that are separated according to kind, polyamide 1010 resin and the molecular weight of the polymer B except polyamide 1010 resin of polyamide 1010 resin, polymer B except polyamide 1010 resin, the difference of the concentration of the kind of organic solvent, polyamide 1010 resin and the polymer B except polyamide 1010 resin, the temperature that carry out an invention, pressure and difference.

In order to obtain the condition that is easy to form phase-separated state, the difference of the solubility parameter of preferred polyamide 1010 resins and the polymer B except polyamide 1010 resin (following, to be sometimes referred to as SP value) is large.

Now, poor as SP value, is 1 (J/cm ³) ^1/2above, 2 (J/cm more preferably ³) ^1/2above, 3 (J/cm more preferably ³) ^1/2above, be particularly preferably 5 (J/cm ³) ^1/2above, be extremely preferably 8 (J/cm ³) ^1/2above.If SP value is this scope, be easy to easily be separated.

As long as the two is dissolved in polyamide 1010 resin and polymer B except polyamide 1010 resin in organic solvent, be not particularly limited, the upper limit as the difference of SP value, is preferably 20 (J/cm ³) ^1/2below, 15 (J/cm more preferably ³) ^1/2below, 10 (J/cm more preferably ³) ^1/2below.

Here so-called SP value, the value calculating for the predication method based on Fedor, based on cohesive energy density(CED) and molar volume calculate (following, be sometimes referred to as computing method.) (" と Meter calculation method for SP value base Foundation ying " Yamamoto show tree work, the apparatus of information of Co., Ltd., puts down into distribution on March 31st, 17).

In the situation that can not calculating by present method, the laboratory method that can whether dissolve by the judgement solvent known with respect to solubility parameter is calculated SP value and (below, is sometimes referred to as laboratory method.), use it to replace (" Polymer Handbook Fourth Edition " J.Brand work, the distribution in 1998 of Wiley society).

In order to select to form the condition of phase-separated state, can be judged by ternary phase diagrams, described ternary phase diagrams can by make polyamide 1010 resin, polymer B except polyamide 1010 resin and dissolve they this ternary ratio vary of organic solvent the simple preliminary experiment observed of state make.

About making phasor, make polyamide 1010 resin, polymer B except polyamide 1010 resin and solvent with ratio mixed dissolution arbitrarily and carrying out when standing, with at least 3 above, be preferably that above, more preferably 10 above points judge whether to produce interface at 5, strict differences is separated into the region of two-phase and becomes the region of 1 phase, thereby can determine the condition that forms phase-separated state.

Now, in order to take a decision as to whether phase-separated state, polyamide 1010 resin, polymer B except polyamide 1010 resin will implemented under temperature of the present invention, pressure, be adjusted to after the ratio of polyamide 1010 resin, polymer B and solvent arbitrarily, polyamide 1010 resin, the polymer B except polyamide 1010 resin are dissolved completely, after dissolving, stir fully, place 3 days, in macroscopic view, be confirmed whether to be separated.Yet, in the situation that form fully stable emulsion, even if sometimes place and within 3 days, also do not carry out being separated in macroscopic view.In this case, use opticmicroscope, phase contrast microscope etc., by whether being separated on microcosmic to judge, be separated.

Be separated is to take by being separated in organic solvent that polyamide 1010 resin is main polyamide 1010 resin solution phase and the polymer B of take except polyamide 1010 resin is that the polymer B solution phase except polyamide 1010 resin of leading forms.Now, polyamide 1010 resin solution phase is the phase that is mainly assigned polyamide 1010 resin, the polymer B of take except polyamide 1010 resin is that master's the polymer B solution phase except polyamide 1010 resin is that the phase that is mainly assigned the polymer B except polyamide 1010 resin (is sometimes referred to as polymer B solution phase below.)。Now, polyamide 1010 resin solution phase and polymer B solution phase have kind and the corresponding volume ratio of usage quantity with polyamide 1010 resin, polymer B except polyamide 1010 resin.

As obtaining the state being separated, and the industrial concentration that can implement, concentration with respect to the polyamide 1010 resin of organic solvent, polymer B except polyamide 1010 resin, although as long as prerequisite is in can being dissolved in the scope of organic solvent, but with respect to total mass, preferably be respectively and surpass 1 quality % and be less than or equal to 50 quality %, be more preferably respectively and surpass 1 quality % and be less than or equal to 30 quality %, be further preferably respectively 2 quality %～20 quality %.

About this two alternate interfacial tension of the polyamide 1010 resin solution phase in the present invention and polymer B solution phase, because two-phase is all organic solvent, therefore its interfacial tension is little, and the emulsion generating due to this character can stably maintain, so size distribution diminishes.Particularly, when the organic solvent of polyamide 1010 resin solution phase and polymer B solution phase is identical, this effect is remarkable.

About two alternate interfacial tensions in the present invention, because interfacial tension is too small, therefore can not be by direct mensuration the such as sessile drop method that add different types of solution to measure in normally used solution, but can calculate by each and the surface tension of air, estimate thus interfacial tension.Each and the surface tension of air are being made as to r ₁, r ₂time, its interfacial tension r _1/2can be by r _1/2=r ₁-r ₂absolute value calculate.Now, this r _1/2preferable range for surpassing 0 and be less than or equal to 10mN/m, more preferably surpass 0 and be less than or equal to 5mN/m, more preferably surpass 0 and be less than or equal to 3mN/m, be particularly preferably and surpass 0 and be less than or equal to 2mN/m.

By using the system that can be separated of such acquisition, the liquid-phase mixing that has made to be separated, after emulsion, contacts with poor solvent, thereby manufactures polyamide 1010 resin particle.

When carrying out micronize, in common reactive tank, implement emulsion formation and (below, be sometimes referred to as micronize operation with the operation contacting with poor solvent.)。

In the method for the manufacture polyamide 1010 resin particle the present invention relates to, in its industrial operating aspect, the easiness consideration forming from emulsion, the temperature that forms emulsion is more than 100 ℃.As the upper limit, so long as the temperature that polyamide 1010 resin and the polymer B except polyamide 1010 resin are dissolved and be separated, and can obtain polyamide 1010 resin particle, just be not particularly limited, be generally the scope of 100 ℃～300 ℃, be preferably 100 ℃～280 ℃, more preferably 120 ℃～260 ℃, more preferably 120 ℃～240 ℃, be particularly preferably 120 ℃～220 ℃, most preferably be the scope of 120 ℃～200 ℃.

About polyamide 1010 resin particle, from the viewpoint of material behavior raising, sometimes require the particle of narrow particle size distribution.

For such requirement; the temperature control forming in the operation (micronize operation) then contacting with poor solvent after emulsion is effective; as its temperature; be generally the scope of 100 ℃～300 ℃; be preferably 100 ℃～280 ℃, more preferably 120 ℃～260 ℃, more preferably 120 ℃～240 ℃; be particularly preferably 120 ℃～220 ℃, most preferably be the scope of 120 ℃～200 ℃.Wherein, from the management easiness of manufacturing process, be preferably the temperature identical with emulsion formation temperature.

Polyamide 1010 resin particle needs to design accordingly with the situation as materials'use the surface shape of particle sometimes, particularly in order to improve the mobility of powder, or the sliding of raising powder, or raising sense of touch, the control of surface shape is important, sometimes require not only narrow particle size distribution, and more to heavens spherical shape particulate.

In the face of such requirement, in the present invention, in order to make this particle shape ball, can be by the temperature of emulsion chemical industry order and micronize operation be controlled ball more to heavens as follows.

; in the high temperature of decrease temperature crystalline temperature that is compared to the thermal property of polyamide 1010 resin, carry out emulsion formation and the operation contacting with poor solvent; carry out micronize, thereby size-grade distribution further narrowed down, and can obtain spherical shape more to heavens particulate.

Here, so-called decrease temperature crystalline temperature, refer to the Tc of measuring by means of differential scanning calorimetry assay method (DSC method), refer to that the heat-up rate with 20 ℃/min heats up after 1 time to the temperature range of comparing the temperature that surpasses 30 ℃ with the fusing point of this polymkeric substance at 30 ℃, keep after 1 minute, while being cooled to 0 ℃ with 20 ℃/min, the summit of the exothermic peak observing.

Be suitable for implementing pressure of the present invention, viewpoint from industrial realization, scope for atmospheric pressure state～100 normal atmosphere (10.1MPa), be preferably the scope of 1 normal atmosphere (101.3kPa)～50 normal atmosphere (5.1MPa), more preferably 1 normal atmosphere (101.3kPa)～30 normal atmosphere (3.0MPa), is particularly preferably 1 normal atmosphere (101.3kPa)～20 normal atmosphere (2.0MPa).

About the micronize in the present invention; owing to being high temperature province; according to circumstances also can be under high pressure; therefore in being easy to promote the state of the thermolysis of polyamide 1010 resin, polymer B except polyamide 1010 resin, organic solvent, so preferably under trying one's best low state, oxygen concn carries out micronize.Now, the oxygen concn of the atmosphere of reactive tank is preferably below 5 volume %, more preferably, below 1 volume %, more preferably, below 0.1 volume %, more preferably, below 0.01 volume %, is particularly preferably below 0.001 volume %.

In addition, due to the mensuration of micro amount of oxygen concentration difficulty in fact, so oxygen concn is calculated in theory by the oxysome volume concentrations of the volume in reaction vessel, non-active gas, displacement pressure in container and number of times thereof.

In addition, reactive tank is preferably used non-active gas.Be specially nitrogen, helium, argon gas, carbonic acid gas, be preferably nitrogen, argon gas.

In addition,, from preventing the viewpoint of the oxidative degradation of the raw material that micronize is used, can use antioxidant as additive.

As antioxidant, from being that antioxidant, sulphur are that antioxidant, aromatic amine are that antioxidant, sulphur are antioxidant, phosphorous antioxidant etc. to supplement the object interpolation of free radical, can enumerate phenol.

Concrete example as these antioxidants, can enumerate phenol, quinhydrones, p methoxy phenol, benzoquinones, 1,2-naphthoquinones, cresols, catechol, phenylformic acid, hydroxy-benzoic acid, Whitfield's ointment, hydroxy benzenesulfonic acid, 2,5-di-tert-butyl hydroquinone, 6-tertiary butyl meta-cresol, 2,6-ditertbutylparacresol, 4-tert-butyl catechol, 2,4 dimethyl 6 tert butyl phenol, TBHQ, the 2-tertiary butyl-4-methoxyphenol etc.

Concentration about antioxidant, is not particularly limited, but is 0.001～10 quality % with respect to the quality optimization of the polymer B except polyamide 1010 resin, and more preferably 0.01～5 quality %, most preferably is 0.05～3 quality %.

By mixed phase separation system state under such condition, thereby form emulsion.By the solution that is separated to above-mentioned acquisition, apply shearing force, thereby generate emulsion.

The particulate being obtained by manufacturing process as described above becomes the particulate that size distribution is extremely little, this be because, by high temperature carrying out emulsion formation, compare with really not so situation, can obtain further emulsion uniformly.

Therefore, in order to obtain sufficient shearing force for forming emulsion, as long as use, adopt the stirring that known method carried out in the past just enough, can be by adopting the generally well-known methods such as the liquid phase paddling process of agitating vane, the paddling process that adopts successively biaxial mixing machine, the hybrid system that adopts homogenizer, ultrasonic irradiation to mix.

Particularly, in the situation that adopt the stirring of agitating vane, although relevant with the shape of agitating vane, but stirring velocity is preferably 50rpm～1,200rpm, more preferably 100rpm～1,000rpm, more preferably 200rpm～800rpm, is particularly preferably 300～600rpm.

As agitating vane, particularly, can enumerate propeller-type, oar type, flat oar type, Scroll-type, bicone, single tapered, monozonal, bizonal, screw type, ribbon type etc., as long as can apply fully shearing force to system, they are not particularly limited.In addition,, in order to carry out efficient stirring, baffle plate etc. can also be set in groove.

In addition, in order to produce emulsion, not only can use stirrer, the device that can also use mulser, dispersion machine etc. to be generally widely known by the people.If illustration particularly, can enumerate homogenizer (IKA society system), polytron homogenizer (キ ネ マ ティ カ society system), the intermittent type mulsers such as the automatic homogeneous mixer of TK (special machine chemical industry society system), Ebara Milder dispersion machine (ebara corporatlon society system), TK Filmics stirrer (special machine chemical industry society system), TK Pipeline Homomixer mulser (special machine chemical industry society system), colloidal mill (refreshing Gangパ ンテック society system), Thrasher hog shred, trigonal triangle wet type pulverising mill (Mitsui three pond chemical industry machine society systems), ultrasonic homogenizer, static mixer etc.

The emulsion obtaining is like this supplied to the operation that particulate is separated out then.

In order to obtain polyamide 1010 resin particle, by the poor solvent of polyamide 1010 resin is contacted with the emulsion of being manufactured by above-mentioned operation, thereby with the particle diameter corresponding with emulsion particle diameter, particulate is separated out.

The contact method of poor solvent and emulsion can be both the method that adds emulsion in poor solvent, can be also the method that adds poor solvent in emulsion, but preferably in emulsion, added the method for poor solvent.

Now, as the method that drops into poor solvent, as long as can obtain polyamide 1010 resin particle, be not particularly limited, can be continuous dripping method, portion-wise addition method, any method in additive process in the lump, for fear of emulsion aggegation when adding poor solvent, fusion, merging and size distribution becomes large or be easy to generate the block that surpasses 1000 μ m, be preferably continuous dripping method, dripping method in batches, in order to implement efficiently industrial, most preferably be continuous dripping method.

In addition as the time that adds poor solvent, be in 10 minutes above 50 hours, in more preferably 30 minutes above 10 hours, more preferably in 1 hour above 5 hours.

If implemented than short time of this scope, sometimes along with the aggegation of emulsion, fusion, merging and size distribution becomes large, or generate block.In addition, in the situation that this implemented for long periods more than scope, in the situation that considering industrial implementation, is unpractical.

By carrying out in this time range, when converting polyamide 1010 resin particle to by emulsion, can suppress interparticle aggegation, can obtain the polyamide 1010 resin particle that size distribution is little.

Although the amount of the poor solvent adding is relevant with the state of emulsion, but with respect to emulsion gross weight 1 mass parts, be preferably 0.1 mass parts～10 mass parts, 0.1 mass parts～5 mass parts more preferably, 0.2 mass parts～3 mass parts more preferably, be particularly preferably 0.2 mass parts～2 mass parts, most preferably be 0.2 mass parts～1.0 mass parts.

The duration of contact of poor solvent and emulsion, so long as for particulate is separated out the sufficient time, but separate out fully and obtain efficient productivity in order to cause, for at poor solvent, add finish after 5 minutes～50 hours, in more preferably 5 minutes above 10 hours, more preferably, in 10 minutes above 5 hours, be particularly preferably 20 minutes above 4 hours in, most preferably be 30 minutes above 3 hours in.

The polyamide 1010 resin particle dispersion of making like this, can carry out solid-liquid separation by generally well-known methods such as filtration, filtration under diminished pressure, pressure filtration, centrifugation, centrifuging, spraying are dried, thereby reclaim particulate powder.

The polyamide 1010 resin particle of solid-liquid separation washs with solvent etc. as required, thereby removes attachment removal or the impurity that contains etc., refines.

In method of the present invention, advantage point is to carry out recirculation, and this recirculation effectively utilizes isolated organic solvent and the polymer B except polyamide 1010 resin in the solid-liquid separation process carrying out when obtaining particulate powder again.

Now, carrying out aspect recirculation, organic solvent and the polymer B except polyamide 1010 resin are in a series of particulate manufacturing process, and the variation of inhibitory substance becomes and continues the stable important document of manufacturing.If use method of the present invention, can suppress up to now the variation as the polymer B except polyamide 1010 resin of problem, even if therefore there is the recirculation of carrying out organic solvent and the polymer B except polyamide 1010 resin, each manufactures the also not variation of batch quality, can stably manufacture such advantage.

The solvent being obtained by solid-liquid separation is the mixture of polymer B, organic solvent and poor solvent except polyamide 1010 resin.By remove poor solvent from this solvent, thereby can be used as the solvent that emulsion forms use, recycle.As the method for removing poor solvent, with generally well-known method, carry out, particularly can enumerate simple distillation, underpressure distillation, precise distillation, thin film distillation, extraction, membrane sepn etc., but be preferably the method for simple distillation, underpressure distillation, precise distillation.

When carrying out the distillation procedures such as simple distillation, underpressure distillation, same while manufacturing with polyamide 1010 resin particle, system is heated, may promote the polymer B except polyamide 1010 resin, the thermolysis of organic solvent, therefore preferably under the state that as far as possible there is no oxygen, carry out, more preferably under nonactive atmosphere, carry out.Particularly, preferred implementation and operation under nitrogen, helium, argon gas, carbon dioxide conditions.In addition, can add again phenol system compound as antioxidant.

When carrying out recirculation, preferably remove poor solvent, particularly as far as possible, the remaining quantity of poor solvent is below 10 quality % with respect to carrying out the organic solvent of recirculation and the total amount of polymer B, be preferably below 5 quality %, more preferably, below 3 quality %, be particularly preferably below 1 quality %.In the situation that surpassing this scope, it is large that the size distribution of polyamide 1010 resin particle becomes, or particles aggregate, therefore not preferred.

The amount of the poor solvent in the solvent of using in recirculation can be measured by generally well-known method, can pass through the mensuration such as vapor-phase chromatography, karl fischer method.

In the operation of removing poor solvent, organic solvent, the losses such as polymer B except polyamide 1010 resin in fact sometimes, the therefore preferred ratio of components of suitably readjusting the initial stage.

The polyamide 1010 resin particle being obtained by the present invention is like this compared with the polyamide 1010 resin particle that the method by the past obtains, because powder fluidity is excellent, therefore can obtain smooth sense of touch, due to the crystalline growth of polyamide 1010 resin, therefore lightness is high, owing to being surface smoothness and ball, be therefore preferred for the purposes of the properties-correcting agent of cosmetic use, coating.

Thus, the polyamide 1010 resin particle being obtained by the present invention is industrially exceedingly useful in various uses and can utilize in practical.Particularly, can be for cleansing milk, sun-screening agent, makeup removing agent, astringent, emulsion, beauty liquid, emulsifiable paste, cold cream, aftershave lotion, shaving soap, paper deoils, the skin care products additives such as the clean skin agent of control oil, foundation cream, white powder, at the bottom of pigment, Mascara, face powder, oiliness powder enamel, eyebrow pencil, Mascara, informer, eye shadow, eye shadow bottoming frost, nose shadow, lipstick, lip gloss, kermes, black dose of tooth (tooth blackening agent), nail varnish, the makeup such as bright nail polish or its properties-correcting agent, shampoo, dry-cleaning shampoo, hair conditioner, hair dye, two-in-one shampoo, hair-care agent, hair tonic, hairspray, hair oil, send out fat, the additive of the hair products such as hair dye, perfume, Gu Longshui, B.O. deodorant, toilet powder shui for baby, toothpaste, collutory, lipstick, the additive of the comfortable product such as perfumed soap, ink powder additive, the rheological modifiers of coating etc., medical-diagnosis checks agent, to automotive material, the mechanical characteristics modifying agent of the products formeds such as material of construction, film, the mechanical characteristics modifying agent of fiber etc., rapid shaping, the resin-formed body raw material of quick manufacture etc., flash molding material, plastisol resin paste, powder adhesion agent, the fluidity amendment of powder, lubricant, rubber ingredients, abrasive, tackifier, filtering medium and filtration adjuvant, gelating agent, flocculation agent, additive for coatings, oil absorber, releasing agent, the smoothness rising agent of plastic film, anti blocking agent, gloss conditioning agent, delustring machining agent, light diffusing agent, high surface hardness rising agent, toughness improves the various properties-correcting agent such as material, liquid crystal indicator pad, chromatographic grade packing material, makeup foundation cream base material additive, microcapsule used additives, the medical material of delivery system/diagnosis medicine etc., the retention agent of spices/agricultural chemicals, catalyzer and its carrier for chemical reaction, adsorbent, pottery processing agglomerated material, measure/analyze the standard particle of use, the particle that field of food industry is used, used for powder coating material, electronic photo developing toner etc.

In addition, by usining polyamide 1010 resin particle that the polyamide 1010 resin of the raw material manufacture that derives from biomass forms due to the properties of materials having as low environmental load, the possibility therefore with the polymer particles that replacement used in the past, as above-mentioned resin-formed body, film, the concrete purposes of fiber etc., for example can enumerate, with the shell of electrical equipment, the shell of OA equipment, various lids, various gears, various shells, sensor, LED lamp, junctor, socket, resistor, relay1 case, switch, various terminal strips, plug, printed wiring board, tuner, loud speaker, microphone, head type headphones, pony pump, head base, power model, shell, semi-conductor, liquid crystal, FDD bracket, FDD chassis, motor brush holder, parabolic antenna, computer associated components etc. are the electrical and electronic parts of representative, with television components, flatiron, hair dryer, electric cooker parts, microwave oven component, sound part, audio frequency-laser disk (registered trademark)-speech ciphering equipment parts such as CD, photographic camera, VTR, the photography lens of projection TV etc., viewfinder, wave filter, prism, the video equipment associated member of Fresnel lens etc., illuminace component, parts of refrigerator, air supply rate, type-writer, word processor parts etc. are the family of representative, office electric product parts, office computer associated components, telephone set associated components, facsimile recorder associated components, duplicating machine associated components, the substrate protection film of various dishes, Disc player pickup lens, optical fiber, photoswitch, the information machine connection parts of optical connector etc., liquid-crystal display, flat-panel monitor, the light guiding plate of plasma display, Fresnel lens, Polarizer, polarization board protective film, phase retardation film, optical diffusion film, field angle is amplified film, reflectance coating, antireflection film, antiglare film, brightness improves film, prismatic lens, touch panel light guiding film, cleaning instrument, motor component, lighter, the mechanical associated components that type-writer etc. are representative, with microscope, binoculars, the optical device that clock and watch etc. are representative, precision optical machinery associated components, fuel is associated, exhaust system, the various pipes of inlet system, inlet mouth nozzle ventpipe, intake manifold, petrolift, safety fuse junctor, loudspeaker terminal, parts of electric insulcrete, lamp socket, lamp reflector, lampshade, engine oil filter and portfire shell etc., very effective in these various uses.

Embodiment

Below, based on embodiment, explain the present invention, but the present invention is not limited to this.

(1) median size and particle size distribution measuring method

Polyamide 1010 resin particle is (following, being sometimes referred to as particle) particle diameter is separately to utilize scanning electron microscope (the scanning electron microscope JSM-6301NF processed of Jeol Ltd.), and length is observed and measured to particle with 1000 times.In addition, at particle, not just justifying in the situation that, measure major diameter as its particle diameter.Median size is by from photo, any 100 particle dias being measured to length, obtains that its arithmetical mean calculates.

The size distribution index that shows size distribution is calculated the value of each particle dia of above-mentioned acquisition based on following numerical value change type (2).

[mathematical expression 2]

$\mathrm{Dn}=\underset{i=1}{\overset{n}{\mathrm{\Σ}}}\mathrm{Ri}/n$

$\mathrm{Dv}={\underset{i=1}{\overset{n}{\mathrm{\Σ}}}\mathrm{Ri}}^4/\underset{i=1}{\overset{n}{\mathrm{\Σ}}}{\mathrm{Ri}}^3$

PDI=Dv/Dn

Wherein, Ri: particle particle dia separately, n: measure several 100, Dn: number average bead diameter, Dv: volume average particle size, PDI: size distribution index.

(2) wide-angle x-ray grating spectrum measuring method

Use the リ ガ of Co., Ltd. Network RINT2100Ultima/PC processed, measure X-ray diffraction.Condition determination is as described below.

X ray gamma ray source: copper K alpha-ray, tube voltage: 40kV, tube current: 30mA

Wavelength: sweep velocity: 3.0 °/min

Divergent slit: 1 °, scatter slit: 1 °, receive slit: 0.15mm

(3) mensuration of degree of sphericity

Degree of sphericity, for utilizing scanning electron microscope to observe particle, is measured minor axis and major diameter, by the mean value of 30 Arbitrary Particles, according to above-mentioned mathematical expression (1), is calculated.In above-mentioned mathematical expression (1), n: measure several 30.

(4) evaluation of surface smoothness

Utilize scanning electron microscope (the scanning electron microscope JSM-6301NF processed of Jeol Ltd.), observe particles with 1000 times, the surperficial observation photo by the particle of gained, carries out visual judgement according to following benchmark.

A: surface smoothing, does not almost have concavo-convex.

B: although surface smoothing, every 1 particle have 10 following concavo-convex.

C: on surface, every 1 particle has and surpasses 10 concavo-convex.

D: air spots is sliding.

(5) evaluation of powder fluidity

As the evaluation of powder fluidity, carry out the mensuration at slope of repose.The measuring method at slope of repose is, uses funnel from the position apart from elevation of water 6cm, particle 5g to be fallen naturally, makes build-up of particles on horizontal plane, utilizes the injection method of the crest line angulation of measuring horizontal plane and particle powder to carry out the mensuration at slope of repose.The powder fluidity of the particle that slope of repose is large is poor, and the mobility of the particle that slope of repose is little is excellent.Slope of repose is that in 25 ° of following situations, powder fluidity is good.

(6) evaluation of the rigidity of particle

Use the micro-compression testing machine MCTW-500 of Shimadzu Scisakusho Ltd's system, in Buddha's warrior attendant plane pressure head made of stones (φ=50 μ m), the load speed 0.3874mN/s of load speed certain way, 23 ℃ of room temperatures, in the standard chamber of humidity 50%RH, measure the Young's modulus of particle.

In addition, following formula 3 and formula 4 are used in calculating of the Young's modulus of particle, for the stand (platform) of cancellation element and the impact of pressure head, according to following formula 3 and formula 4, by the E as particle Young's modulus ₁calculate.

E ₁: the Young's modulus of particle (GPa)

E ₂: the Young's modulus (1140GPa) of device pressure head

E ₃: the Young's modulus (200GPa) of device stand (platform)

N ₁: the Poisson's ratio of particle (being made as 0.4)

N ₂: the Poisson's ratio (0.07) of device pressure head

N ₃: the Poisson's ratio of apparatus platform (0.3)

δ: the compression displacement (μ m) during particle compression

E ^*: with the complex elastic-modulus (GPa) of determination object

R ₁: the radius of particle (μ m)

P: loading (mN)

[mathematical expression 3]

${\mathrm{\δ}}^3=\frac{9}{16R_1}{E}^{*}{P}^2$

[mathematical expression 4]

$E^{*}={[{(\frac{1-{v_1}^2}{E_1}+\frac{1-{v_2}^2}{E_2})}^{\frac{2}{3}}+{(\frac{1-{v_1}^2}{E_1}+\frac{1-{v_3}^2}{E_3})}^{\frac{2}{3}}]}^3$

In addition, when calculating Young's modulus, be used as the data point of deformed region of 1-5% of the particle dia in recoverable deformation region, calculate.

(7) bulk density

Particle is filled to quietly in the graduated cylinder of 10ml, measures the weight of the particle in graduated cylinder, obtain the quality of per unit volume, be made as bulk density.

(8) sense of touch

Use the particle of gained, by 8 group members, implement sensory evaluation.Evaluation method is, particle a small amount of (0.02g left and right) is put in to the back of the hand of a hand, and 3 finger friction particles with another hand, carry out sensory test to " foreign body sensation ", " flexibility ", " slipperiness " these 3 projects.For each project, the average mark of 8 people when marking as following adopts following basis point grade.

" foreign body sensation "

3 minutes: there is no foreign body sensation

2 minutes: have a little foreign body sensation

1 minute: have foreign body sensation

" flexibility "

3 minutes: soft sense of touch

2 minutes: soft a little sense of touch

1 minute: hard sense of touch

" slipperiness "

3 minutes: smooth

2 minutes: smooth a little

1 minute: draw extension

< determinating reference >

9.0～6.5 are divided into zero

6.4～4.5 are divided into △

4.4～3.0 be divided into *

(9) mensuration of lightness

With the beam splitting type chromascope processed SE-2000 of Japanese electricity Se Industrial Co., Ltd, carry out the mensuration of lightness L.As benchmark, the standard white plate (y=95.99, x=94.04, z=113.10) that using appts is subsidiary.

(10) quantivative approach of the contained sodium acetate of polyvinyl alcohol

The sodium acetate of recording by Japanese Industrial Standards' " polyvinyl alcohol test method " (K6726-1994 year) dissolves volumetry to be measured.

Washing 1 > of the sodium acetate in reference example 1 < polyvinyl alcohol

In the eggplant type flask of 1L, and interpolation polyvinyl alcohol (the Nippon Synthetic Chemical Industry Co., Ltd's G type processed ‘ ゴ ー セ ノ ー Le (registered trademark) ' GM-14 weight-average molecular weight 29,000, SP value 32.8 (J/cm ³) ^1/2, sodium acetate content 0.23 quality %) and 50g, methyl alcohol 500ml, at room temperature stir 1 hour.Then, by suction filtration (filter paper 5A, φ 90mm), carry out filtering separation.Same operation is proceeded 2 times, carried out altogether after 3 times, at 80 ℃, be dried 10 hours, thereby obtain the poor polyvinyl alcohol of sodium acetate.Sodium acetate in the polyvinyl alcohol of quantitative gained, result is 0.05 quality %.

The manufacture method > of embodiment 1 < polyamide 1010 resin particle

In the withstand voltage glass autoclave (withstand voltage nitre industry (strain) Ha イ パ ー グ ラ ス タ ー TEM-V1000N) of 1000ml, add polyamide 1010 (weight-average molecular weight 22,500, Hipro Port リマ ー society system ' Hiprolon (registered trademark) '-200) 24.5g, as the METHYLPYRROLIDONE 273.5g of organic solvent, as the few polyvinyl alcohol 42g (weight-average molecular weight 29 of the sodium acetate of being made by reference example 1 of the polymer B except polyamide 1010 resin, 000, SP value, 32.8 (J/cm ³) ^1/2), carry out, after nitrogen replacements more than 99 volume %, being heated to 180 ℃, carry out stirring until polymer dissolution for 2 hours.Now, to count in be below 1% to oxymeter.Then, using the ion exchanged water of the 350g as poor solvent, via transferpump, the speed with 2.91g/ minute drips.In the moment of having added the ion exchanged water of about 110g, system becomes white.Added after the water of whole amounts, under the state stirring, lowered the temperature, the suspension of gained has been filtered, added ion exchanged water 700g and carry out repulped washing, the material filtering to isolate has been carried out to vacuum-drying in 10 hours at 80 ℃, obtained white solid 24.0g.Utilize scanning electron microscope to observe the powder of gained, the particle shape that result is spherical shape (Fig. 7), is median size 7.5 μ m, the polyamide 1010 resin particle of size distribution index 1.12.About this polyamide 1010 resin particle, measure wide-angle x-ray grating spectrum, result is at 20 degree and 24 degree places, to have peak (Fig. 1) in diffraction angle 2 θ.In addition, the fusing point of the polyamide 1010 using in the present embodiment is 207 ℃, and melting heat capacity is 29.0J/g, and decrease temperature crystalline temperature is 144 ℃.SP value is obtained by computing method, is 22.47 (J/cm ³) ^1/2.In addition, the estimated value of the interfacial tension of body series is below 2mN/m.The solubleness (room temperature) of polymeric amide in the water as poor solvent is below 0.1 quality %.

The evaluation result of the characteristic of the polyamide 1010 resin particle of gained is shown in Table 1.The polyamide 1010 resin particle of the present embodiment is that spherical shape and surface smoothness are excellent, and powder fluidity is excellent.

The molecular weight of measuring the polyvinyl alcohol in the filtrate after particlized finishes, result is that weight-average molecular weight is 28,500, with almost not variation before use.

Embodiment 2 < are by the manufacture method > of the polyamide 1010 resin particle of sour interpolation

In the withstand voltage glass autoclave (withstand voltage nitre industry (strain) Ha イ パ ー グ ラ ス タ ー TEM-V1000N) of 1000ml, add polyamide 1010 (weight-average molecular weight 22,500, Hipro Port リマ ー society system ' Hiprolon (registered trademark) '-200) 35g, as the METHYLPYRROLIDONE 273g of organic solvent, as polyvinyl alcohol 42g (the Nippon Synthetic Chemical Industry Co., Ltd's G type processed ' go ー セ ノ ー Le (registered trademark) ' GH-20 of the polymer B except polyamide 1010 resin, weight-average molecular weight 44,600, SP value, 32.8 (J/cm ³) ^1/2) and L-TARTARIC ACID 0.21g, carry out, after nitrogen replacements more than 99 volume %, being heated to 180 ℃, carry out stirring until polymer dissolution for 3 hours.Now, to count in be below 1% to oxymeter.Then, using the ion exchanged water of the 350g as poor solvent, via transferpump, the speed with 2.91g/ minute drips.In the moment of having added the ion exchanged water of about 80g, system becomes white.Added after the water of whole amounts, under the state stirring, lowered the temperature, the suspension of gained has been filtered, added ion exchanged water 700g and carry out repulped washing, the material filtering to isolate has been carried out to vacuum-drying in 10 hours at 80 ℃, obtained white solid 34.5g.Utilize scanning electron microscope to observe the powder of gained, the particle shape that result is spherical shape (Fig. 8), is median size 15.8 μ m, the polyamide 1010 resin particle of size distribution index 1.14.About this polyamide 1010 resin particle, measure wide-angle x-ray grating spectrum, result is at 20 degree and 24 degree places, to have peak (Fig. 2) in diffraction angle 2 θ.In addition, the fusing point of the polyamide 1010 using in the present embodiment is 207 ℃, and melting heat capacity is 29.0J/g, and decrease temperature crystalline temperature is 144 ℃.In addition, the estimated value of the interfacial tension of body series is below 2mN/m.The solubleness (room temperature) of polymeric amide in the water as poor solvent is below 0.1 quality %.

The evaluation result of the characteristic of the polyamide 1010 resin particle of gained is shown in Table 1.The polyamide 1010 resin particle of the present embodiment is that spherical shape and surface smoothness are excellent, powder fluidity, excellent rigidity.

The molecular weight of measuring the polyvinyl alcohol in the filtrate after particlized finishes, result is that weight-average molecular weight is 45,000, with almost not variation before use.

The manufacture method > of embodiment 3 < polyamide 1010 resin particles

In the withstand voltage glass autoclave (withstand voltage nitre industry (strain) Ha イ パ ー グ ラ ス タ ー TEM-V1000N) of 1000ml, add polyamide 1010 (weight-average molecular weight 22,500, Hipro Port リマ ー society system ' Hiprolon (registered trademark) '-200) 35g, as the METHYLPYRROLIDONE 273g of organic solvent, as the few polyvinyl alcohol 42g (weight-average molecular weight 29 of the sodium acetate of being made by reference example 1 of the polymer B except polyamide 1010 resin, 000, SP value, 32.8 (J/cm ³) ^1/2), carry out, after nitrogen replacements more than 99 volume %, being heated to 180 ℃, carry out stirring until polymer dissolution for 2 hours.Now, to count in be below 1% to oxymeter.Then, using the ion exchanged water of the 350g as poor solvent, via transferpump, the speed with 2.91g/ minute drips.In the moment of having added the ion exchanged water of about 110g, system becomes white.Added after the water of whole amounts, under the state stirring, lowered the temperature, the suspension of gained has been filtered, added ion exchanged water 700g and carry out repulped washing, the material filtering to isolate has been carried out to vacuum-drying in 10 hours at 80 ℃, obtained white solid 34.0g.Utilize scanning electron microscope to observe the powder of gained, the particulate form that result is spherical shape (Fig. 9), is median size 11.8 μ m, the polyamide 1010 resin particle of size distribution index 1.21.The degree of sphericity of this polyamide 1010 resin particle is 90, measures wide-angle x-ray grating spectrum, and result is at 20 degree and 24 degree places, to have peak (Fig. 3) in diffraction angle 2 θ.

In addition, the fusing point of the polyamide 1010 using in the present embodiment is 207 ℃, and melting heat capacity is 29.0J/g, and decrease temperature crystalline temperature is 144 ℃.SP value is obtained by computing method, is 22.47 (J/cm ³) ^1/2.In addition, the estimated value of the interfacial tension of body series is below 2mN/m.The solubleness (room temperature) of polymeric amide in the water as poor solvent is below 0.1 quality %.

The evaluation result of the characteristic of the polyamide 1010 resin particle of gained is shown in Table 1.The polyamide 1010 resin particle of the present embodiment is that spherical shape and surface smoothness are excellent, powder fluidity, excellent rigidity.

The molecular weight of measuring the polyvinyl alcohol in the filtrate after particlized finishes, result is that weight-average molecular weight is 28,500, with almost not variation before use.

Comparative example 1

Method based on patent documentation 1 (TOHKEMY 2007-277546 communique), produces polyamide 1010 resin particle.By polyamide 1010 (weight-average molecular weight 22,500, Hipro Port リマ ー society system ' Hiprolon (registered trademark) '-200) 24.0g, oligosaccharides (the system reduction β-amylose compound PO-10 of Mitsubishi フー ドテック society) 40.0g, tetramethylolmethane 16.0g be added in the Labo Plasto Mill of 230 ℃, with the speed of rotation of 50 revs/min, carries out 5 minutes melting mixings.After cooling, the block of gained is added in ion exchanged water, at 60 ℃, washs, the material filtering to isolate is carried out to vacuum-drying in 10 hours at 80 ℃, obtain the brown solid 21.0g of powder shaped.

Utilize scanning electron microscope to observe the powder of gained, the particle shape that result is smooth-flat-surface (Figure 10), is median size 7.0 μ m, size distribution index 12.59.About this polyamide 1010 resin particle, measure wide-angle x-ray grating spectrum, although observe peak at 20 degree places in result diffraction angle 2 θ, at 24 degree places, do not observe peak (Fig. 4).The evaluation of the characteristic of the polyamide 1010 resin particle of gained is shown in Table 1.The lightness of the particle of gained is low, and powder fluidity is poor.

Comparative example 2

Method based on patent documentation 2 (TOHKEMY 2010-163618 communique), produces polyamide 1010 resin particle.In the withstand voltage glass autoclave (withstand voltage nitre industry (strain) Ha イ パ ー グ ラ ス タ ー TEM-V1000N) of 1000ml, add polyamide 1010 (weight-average molecular weight 22,500, Hipro Port リマ ー society system ' Hiprolon (registered trademark) '-200) 56.5g, as the ethanol 280g of organic solvent, carry out after nitrogen replacements more than 99 volume %, be heated to 155 ℃, with slurry type agitating vane, with the speed of rotation of 250 revs/min, carry out stirring until polymer dissolution for 1 hour.Then, ethanol continuously distilled remove be on one side cooled to 125 ℃ on one side, carry out stirring for 1 hour.Then, while stir in the moment that is cooled to 120 ℃ and start separating out of resin.Ethanol distillation is removed, after 25 minutes, in the moment of separating out end of resin, while stir, lowered the temperature simultaneously, take out the powder of separating out, at 50 ℃, carry out vacuum-drying in 10 hours, obtain white solid 53g.Utilize scanning electron microscope to observe the powder of gained, the irregular particle shape (Figure 11) that result is Porous, is median size 149 μ m, size distribution index 30.7.About this polyamide 1010 resin particle, measure wide-angle x-ray grating spectrum, result is at 20 degree and 24 degree places, to have peak (Fig. 5) in diffraction angle 2 θ, but median size, degree of sphericity are outside scope given to this invention.The evaluation result of the characteristic of the polyamide 1010 resin particle of gained is shown in Table 1.The particle of gained has coarse, and powder fluidity is poor.

Comparative example 3

Use SPEX society freezing crusher processed (Freezer Mill) 6750, by polyamide 1010 (weight-average molecular weight 22,500, Hipro Port リマ ー society system ' Hiprolon (registered trademark) '-200) 16g in liquid nitrogen grinding time 2 minutes, knocker number of times 20 times/second, freezing and pulverizing under the condition that pulverizing number of times is 3 times, the powder of acquisition polyamide 1010 resin.Utilize scanning electron microscope to observe the powder of gained, the powder that result is shape at random (Figure 12), median size is 434 μ m, size distribution index is 2.15.About the powder of this polyamide 1010, measure wide-angle x-ray grating spectrum, result is at 24 degree places, not observe peak (Fig. 6) in diffraction angle 2 θ.The evaluation result of the characteristic of the polyamide 1010 resin powder of gained is shown in Table 1.The powder of gained is not owing to being spherical, and therefore coarse large, because particle diameter is inhomogeneous, so powder fluidity is poor.

Industry utilizability

The present invention can be applicable to require surface smoothness excellent, and spherical shape and powder fluidity are good, all purposes of the polyamide 1010 resin particle of excellent rigidity.

Claims (18)

1. a polyamide 1010 resin particle, is characterized in that, median size is 1～100 μ m, and degree of sphericity is more than 80, through wide-angle x-ray scattering, measure, and at diffraction angle 2 θ, be that 24 degree places have peak.

2. polyamide 1010 resin particle according to claim 1, is characterized in that, through wide-angle x-ray scattering, measure, and at diffraction angle 2 θ, be that 20 degree and 24 degree places have peak.

3. polyamide 1010 resin particle according to claim 1 and 2, is characterized in that, the slope of repose of powder is below 30 °.

4. according to the polyamide 1010 resin particle described in any one of claim 1～3, it is characterized in that, the compressive modulus of elasticity of the particle being obtained by micro-compression testing machine is more than 1.6GPa.

5. according to the polyamide 1010 resin particle described in any one of claim 1～4, it is characterized in that, while measuring with beam splitting type chromascope, lightness L value is more than 70.

6. the manufacture method of a polyamide 1010 resin particle, it is characterized in that, make can be separated into after polyamide 1010 resin, polymer B except polyamide 1010 resin and organic solvent dissolution are mixed using polyamide 1010 resin as the solution phase of principal constituent and the polymer B of usining except polyamide 1010 resin the System forming emulsion as this two-phase of solution phase of principal constituent, then make this emulsion contact with the poor solvent of polyamide 1010 resin, polyamide 1010 resin is separated out

In more than 100 ℃ temperature, implement the formation of emulsion.

7. the manufacture method of polyamide 1010 resin particle according to claim 6, is characterized in that, the SP value of the polymer B except polyamide 1010 resin is 20 (J/cm ³) ¹/ ²above.

8. according to the manufacture method of the polyamide 1010 resin particle described in claim 6 or 7, it is characterized in that, the solubleness in water in the time of 25 ℃ of the polymer B except polyamide 1010 resin is more than 1g/100g.

9. according to the manufacture method of the polyamide 1010 resin particle described in any one of claim 6～8, it is characterized in that, the polymer B except polyamide 1010 resin in its molecular skeleton, have in hydroxyl, ether, amide group, carboxyl at least any.

10. according to the manufacture method of the polyamide 1010 resin particle described in any one of claim 6～9, it is characterized in that, the polymer B except polyamide 1010 resin is any in polyvinyl alcohol, hydroxy alkyl cellulose, polyalkylene glycol, polyvinylpyrrolidone, water-soluble nylon, polyacrylic acid.

11. according to the manufacture method of the polyamide 1010 resin particle described in any one of claim 6～10, it is characterized in that, the polymer B except polyamide 1010 resin is polyvinyl alcohol, and the sodium acetate content in polyvinyl alcohol is below 0.1 quality %.

12. according to the manufacture method of the polyamide 1010 resin particle described in any one of claim 6～10, it is characterized in that, the polymer B except polyamide 1010 resin is polyvinyl alcohol, adds acid compound when emulsion forms in system.

The manufacture method of 13. polyamide 1010 resin particles according to claim 12, is characterized in that, the acid compound adding is that the 1st dissociation index pKa1 is the acid below 4.5, more than the boiling point that its decomposition temperature is poor solvent.

14. according to the manufacture method of the polyamide 1010 resin particle described in claim 12 or 13, it is characterized in that, the acid compound adding be selected from citric acid, tartrate, propanedioic acid, oxalic acid, hexanodioic acid, toxilic acid, oxysuccinic acid, phthalic acid, succsinic acid, polyacrylic acid more than a kind.

15. according to the manufacture method of the polyamide 1010 resin particle described in any one of claim 6～14, it is characterized in that, the SP value of organic solvent is 20 (J/cm ³) ^1/2above and boiling point be more than 100 ℃.

16. according to the manufacture method of the polyamide 1010 resin particle described in any one of claim 6～15, it is characterized in that, organic solvent is for being selected from N-Methyl pyrrolidone, methyl-sulphoxide, N, dinethylformamide, N, N-N,N-DIMETHYLACETAMIDE, 1, in 3-dimethyl-2-imidazolidone more than a kind.

17. according to the manufacture method of the polyamide 1010 resin particle described in any one of claim 6～16, it is characterized in that, after emulsion forms, for polyamide 1010 resin is separated out, temperature more than the decrease temperature crystalline temperature that the temperature while contacting with poor solvent is polyamide 1010 resin.

18. according to the manufacture method of the polyamide 1010 resin particle described in any one of claim 6～17, it is characterized in that, after polyamide 1010 resin is separated out, carry out solid-liquid separation and remove polyamide 1010 resin particle, from the remaining solution that comprises the polymer B composition except polyamide 1010 resin, remove poor solvent, in the solution of gained, again add polyamide 1010 resin, formation can be separated into using polyamide 1010 resin as the solution phase of principal constituent and the polymer B of usining except polyamide 1010 resin the system as this two-phase of solution phase of principal constituent, organic solvent and the polymer B except polyamide 1010 resin are recycled.

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